Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
  • C09D5/024—Emulsion paints including aerosols characterised by the additives
  • C09D5/025—Preservatives, e.g. antimicrobial agents
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0058—Biocides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
  • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D123/04—Homopolymers or copolymers of ethene
  • C09D123/08—Copolymers of ethene
  • C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
  • C09D123/0853—Vinylacetate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
  • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
  • C09D131/04—Homopolymers or copolymers of vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/37—Thiols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
  • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
  • C08K5/47—Thiazoles

Definitions

• the present invention relates to a process for producing aqueous coating compositions, such as adhesives, paints, lacquers and varnishes, containing aqueous polymer dispersions.
• Aqueous polymer dispersions (latex emulsions) and coating compositions containing the same are susceptible to microbial contamination resulting in product spoilage.
• Polymer dispersions are composed of fine organic polymer particles in water. These polymer particles are suspended and stabilized in an aqueous environment with additional organic substrates, such as surfactants and protective colloids.
• surfactants, protective colloids such as poly(vinyl alcohol) and hydroxy ethyl cellulose, thickeners and other additives, as well as the polymer itself provide a supply of carbon nutrition for microorganisms to metabolize. Polymer emulsions are therefore susceptible to spoilage due to microbial attack and propagation.
• Standard industrial practices seek to combat such product biodeterioration by the addition of various industrial biocides (antimicrobial agents) directly after the manufacturing process.
• industrial biocides include 1,2- benzisothiazolin-3-one (BIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CIT), 2-methyl-4- isothiazolin-3-one (MIT) and blends thereof.
• isothiazolinone-based biocides are known to cause allergic contact dermatitis and, in fact, among commercial painters they are one of the most common causes of this medical condition.
• products in Europe containing more than 15 ppm of MIT will soon have to carry the H 317 hazard warning label“May cause an allergic skin reaction”, whereas the limit for this mandate for CIT/MIT (3: 1) is already ⁇ 15 ppm.
• WO 2017/148572 discloses a method of reducing microbial infestation of a product comprising the steps of: (A) providing a product, such as a paint or polymer dispersion and (B) adding to the product 1 to 100 ppm of 5-chloro- 2-methyl-4-isothiazolin-3-one containing 2-methyl -4-isothiazolin-3-one in the range of 0 to 2% by weight, based on the total amount of 5-chloro-2-methyl-4-isothiazolin-3-one, (C) decomposing the 5-chloro-2 -methyl-4-isothiazolin-3-one using at least one 5-chloro-2- methyl-4-isothiazolone-decomposing compound and (D) adding at least one biocide selected from the group consisting of l,2-benzisothiazolin-3-one in an amount of 1 to 1,000 ppm, 2,2- dibromo-3-nitrilopropionamide in an amount in the range of 1 to 2,500
• the invention resides in a process for producing an aqueous coating composition, the process comprising:
• the invention resides in a process for producing an aqueous coating composition, the process comprising:
• the invention also resides in coating compositions, such as adhesives, paints, lacquers and varnishes, produced by the processes described herein.
• the present disclosure relates to the production of aqueous coating compositions, such as adhesives, paints, lacquers and varnishes, from aqueous polymer dispersions, such as those produced by free radical initiated polymerization.
• aqueous coating compositions such as adhesives, paints, lacquers and varnishes
• the present disclosure provides a process in which microbial growth in the polymer dispersion and the final coating composition is effectively inhibited during production and storage of the coating composition by the addition of a specific combination of the biocides, 5-chloro-2-methyl-3(2H)- isothiazolone (CIT), 2,2-dibromo-3-nitrilopropionamide (DBNPA) and optionally 2-methyl- 3(2H)-isothiazolone (MIT).
• CIT 5-chloro-2-methyl-3(2H)- isothiazolone
• DBNPA 2,2-dibromo-3-nitrilopropionamide
• MIT 2-methyl- 3
• the CIT and DBNPA are decomposed either by chemical treatment or by raising the pH of the coating composition or both. Future microbial attack of the coating composition can then be prevented by the addition of a different, less hazardous biocide or by ensuring the pH of the coating composition is in excess of 10.5. In the latter case, the coating composition can be labeled preservative-free.
• the present process comprises providing an aqueous polymer dispersion having a pH ⁇ 7 and adding to the dispersion from 1 to 30 ppm, such as from 5 to 20 ppm, such as from 10 to 14.9 ppm, of CIT, and 10 to 1000 ppm, such as 20 to 400 ppm, such as 50 to 150 ppm, for example about 100 ppm, of DBNPA, all by weight of the total weight of the dispersion.
• at least one adjuvant is added to the dispersion to produce a coating composition, which can then be stored substantially without microbial growth for up to 6 months.
• the pH of the coating composition is raised to a value, typically >8 but preferably less than 10, sufficient to decompose the DBNPA and a compound effective to decompose CIT is added to the coating composition to decompose the CIT.
• Suitable CIT- decomposing compounds include cysteine or derivative thereof, such as N-acetyl cysteine, mercaptoethanol, mercaptopropionic acid, methylmercaptopropionate, glutathione, thioglycolate, sodium thiosulfate, sodium bisulfite, pyrithione, mercaptopyridine, dithiothreitol, mercaptoethanesulfonate, and sodium formaldehyde sulfoxylate, with cysteine being preferred.
• cysteine or derivative thereof, such as N-acetyl cysteine, mercaptoethanol, mercaptopropionic acid, methylmercaptopropionate, glutathione, thioglycolate, sodium thiosulfate, sodium bisulfite, pyrithione, mercaptopyridine, dithiothreitol, mercaptoethanesulfonate, and sodium formaldehyde sul
• the final coating composition reaching the end user is substantially free of such biocides and does not require a label, such as the H 317 hazard warning in Europe.
• less hazardous biocides can be added before release of the coating composition, for example 50 to 300 ppm, preferably 50 to 250 ppm, by weight zinc pyrithrione and/or 50 to 500, preferably 75 to 350 ppm, by weight of l,2-benzisothiazolin-3-one (BIT) and/or 50 to 150 ppm by weight of 2-bromo-2-nitro-l,3- propanediol, all based on the total weight of the coating composition.
• BIT l,2-benzisothiazolin-3-one
• the amount of cysteine added to decompose the CIT will of course depend on the amount of CIT used to preserve the dispersion and coating composition. Generally, however, cysteine is added in a molar ratio of 1:1 to 2:1 with respect to the added CIT.
• the present process again comprises providing an aqueous polymer dispersion having a pH ⁇ 7 and adding to the dispersion 1 to 30 ppm, such as 1 to 20 ppm, such as 1 to 14.9 ppm, of CIT, and 10 to 1000 ppm, such as 20 to 400 ppm, such as 50 to 150 ppm, for example about 100 ppm, of DBNPA, all by weight of the total weight of the dispersion.
• at least one adjuvant is added to the dispersion to produce a coating composition, which can then be stored substantially without microbial growth for up to 6 months.
• the pH of the coating composition is raised to a value of at least 10.5, preferably between 10.5 to 11.5, to decompose the DBNPA and CIT and to preserve the coating composition against microbial attack.
• the final coating composition can therefore be labeled preservative-free, where the term“preservative-free” means that the remaining biocide concentration of each of CIT/ MIT and DBNPA is ⁇ 1 ppm by weight, preferably ⁇ 0.5 ppm by weight.
• up to 10 ppm, such as up to 3ppm, such as up to 1 ppm, of MIT can be added to the polymer dispersion along with the CIT and DBNPA, for example by adding at least part of the CIT in the form of the three-to-one blend of CIT/MIT available from many manufacturers.
• no measurable amount of MIT is added to the polymer dispersion.
• raising the pH of the coating composition to decompose the DBNPA or the DBNPA, the CIT and, where present, the MIT is conveniently effected by adding one or more of an alkali metal hydroxide, an alkali metal silicate, an alkylalkoxysilane, an alkylalkoxysiloxane and an alkysiliconate to the coating composition.
• an alkali metal hydroxide, an alkali metal silicate, an alkylalkoxysilane, an alkylalkoxysiloxane and an alkysiliconate to the coating composition.
• certain adjuvants such as calcium carbonate used as a filler, can also raise the pH of the coating composition but this is generally insufficient to cause significant decomposition of the biocides added as preservatives.
• the aqueous polymer dispersions used in the present process are generally produced by free-radically initiated polymerization of one or more main monomers.
• Suitable main monomers are selected from Ci-C2o-alkyl (meth)acrylates, vinyl esters of carboxylic acids with up to 20 carbons, vinyl- aromatic compounds having up to 20 carbons, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of Ci-Cio alcohols, C2-C8 aliphatic hydrocarbons with 1 or 2 double bonds, and mixtures of these monomers.
• Preferred alkyl (meth)acrylates are Ci-Cio-alkyl (meth)acrylates, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate. Mixtures of alkyl (meth)acrylates can also be employed .
• suitable vinyl esters of C1-C20 carboxylic acids include vinyl acetate, vinyl propionate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl 2-ethyl hexanoate and Versatic acid vinyl esters, with vinyl acetate being particularly preferred.
• Suitable vinyl-aromatic compounds include vinyltoluene, a- and p-methylstyrene, a-butylstyrene, 4-n-butylstyrene, 4-n-decyl-styrene and, preferably, styrene.
• Suitable nitriles include acrylonitrile and methacrylonitrile.
• Suitable vinyl halides include chloro-, fluoro- or bromo-substituted ethylenically unsaturated compounds, such as vinyl chloride and vinylidene chloride.
• vinyl ethers are vinyl methyl ether and vinyl iso-butyl ether, with preference being given to vinyl ethers of C1-C4 alcohols.
• Examples of suitable C2-C8 aliphatic hydrocarbons with one olefinic double bond include ethene and propene, whereas representative examples of C2-C8 aliphatic hydrocarbons having two olefinic double bonds include butadiene, isoprene and chloroprene.
• the present polymer dispersion is produced from a mixture of free-radically polymerizable main monomers comprising from 50 wt% to 99 wt% vinyl acetate and from 1 wt% to 40 wt% ethylene.
• the aqueous polymerization mixture used to produce the present polymer dispersion may comprise up to 10 wt% of auxiliary co-monomer(s) based on the total weight of monomers in the mixture.
• auxiliary co-monomers can be those which promote better film or coating performance by the compositions herein or can provide films and coatings of desirable properties.
• desirable properties can include, for example, enhanced adhesion to surfaces or substrates, improved wet adhesion, better resistance to removal by scrubbing or other types of weathering or abrasion, and improved resistance to film or coating cracking.
• the optional co-monomers useful for incorporation into the emulsion copolymers of the compositions herein are those which contain at least one polymerizable double bond along with one or more additional functional moieties.
• Suitable auxiliary co-monomers include unsaturated organic acids, unsaturated silanes, glycidyl co-monomers, ureido co-monomers, co-monomers with crosslinkable functions, crosslinking co-monomers and combinations thereof.
• Suitable auxiliary co-monomers including unsaturated organic acids comprise ethylenically unsaturated carboxylic acids and anhydrides and amides thereof, ethylenically unsaturated sulfonic acids, and ethylenically unsaturated phosphonic acids.
• the auxiliary monomer may comprise an ethylenically unsaturated C 3 -C 8 monocarboxylic acid and/or an ethylenically unsaturated C 4 -Cs dicarboxylic acid, together with the anhydrides or amides thereof.
• suitable ethylenically unsaturated C3-C8 monocarboxylic acids include acrylic acid, methacrylic acid and crotonic acid.
• suitable ethylenically unsaturated C 4 -Cs dicarboxylic acids include maleic acid, fumaric acid, itaconic acid and citraconic acid.
• Suitable ethylenically unsaturated sulfonic acids include those having 2-8 carbon atoms, such as vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2- acryloyloxyethanesulfonic acid and 2-methacryloyloxyethanesulfonic acid, 2-acryloyloxy- and 3-methacryloyloxypropanesulfonic acid.
• suitable ethylenically unsaturated phosphonic acids also include those having 2-8 carbon atoms, such as vinylphosphonic acid and ethylenically unsaturated polyethoxyalkyletherphosphates.
• the salts thereof preferably the alkali metal or ammonium salts thereof, particularly preferably the sodium salts thereof, such as, for example, the sodium salts of vinylsulfonic acid and of 2- acrylamidopropanesulfonic acid.
• Unsaturated silanes usful as auxiliary co-monomers can generally correspond to the structural Formula I:
• R denotes an organic radical olefinically unsaturated in the co-position and R 1 R 2 and R 3 which may be identical or different, denote the group -OZ, Z denoting hydrogen or primary or secondary alkyl or acyl radicals optionally substituted by alkoxy groups.
• Suitable unsaturated silane compounds of the Formula I are preferably those in which the radical R in the formula represents an w-unsaturated alkenyl of 2 to 10 carbon atoms, particularly of 2 to 4 carbon atoms, or an w-unsaturated carboxylic acid ester formed from unsaturated carboxylic acids of up to 4 carbon atoms and alcohols carrying the Si group of up to 6 carbon atoms.
• Suitable radicals R 1 , R 2 , R 3 are preferably the group -OZ, Z representing primary and/or secondary alkyl radicals of up to 10 carbon atoms, preferably up to 4 carbon atoms, or alkyl radicals substituted by alkoxy groups, preferably of up to 3 carbon atoms, or acyl radicals of up to 6 carbon atoms, preferably of up to 3 carbon atoms, or hydrogen.
• Most preferred unsaturated silane co-monomers are vinyl trialkoxy silanes.
• Examples of preferred silane compounds of the Formula I include g- methacryloxypropyltris(2-methoxyethoxy)silane, vinylmethoxysilane, vinyltriethoxysilane, vinyldiethoxysilanol, vinylethoxysilanediol, allyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltriacetoxysilane, trimethylglycolvinylsilane, g-methacryloxypropyltrimethylglycolsilane, g- acryloxypropyltriethoxysilane and g-methacryloxypropyltrimethoxysilane.
• Glycidyl compounds can also be used as optional auxiliary co-monomers to impart epoxy-functionality to the emulsion copolymer.
• suitable glycidyl optional co-monomers include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and vinyl glycidyl ether.
• Another type of optional co-monomer comprises cyclic ureido co-monomers.
• Cyclic ureido co-monomers are known to impart improved wet adhesion properties to films and coatings formed from copolymers containing these co-monomers.
• Cyclic ureido compounds and their use as wet adhesion promoting co-monomers are disclosed in U.S. Patent Nos. 4,104,220; 4,111,877; 4,219,454; 4,319,032; 4,599,417 and 5,208,285. The disclosures of all of these U.S. patents are incorporated herein by reference in their entirety.
• Another type of optional co-monomer comprises co-monomers with crosslinkable functions such as N-methylolacrylamide, N-methylolmethacrylamide, N- methylolallylcarbamate, N-methylolmaleimide, N-methylolmaleamic acid, and the N- methylol amides of aromatic vinyl carboxylic acids, such as N-methylol-p-vinylbenzamide.
• crosslinkable functions such as N-methylolacrylamide, N-methylolmethacrylamide, N- methylolallylcarbamate, N-methylolmaleimide, N-methylolmaleamic acid, and the N- methylol amides of aromatic vinyl carboxylic acids, such as N-methylol-p-vinylbenzamide.
• a further group of comonomers suitable for preparing the emulsion polymers used herein comprises crosslinking monomers, such as comonomers with polyethylenic unsaturation, and hence with a crosslinking action.
• crosslinking monomers such as comonomers with polyethylenic unsaturation, and hence with a crosslinking action.
• examples include diallyl phthalate, diallyl maleate, trlallyl cyanurate, tetraallyloxyethane, divinylbenzene, butane- l,4-diol dimethacrylate, triethylene glycol dimethacrylate, divinyl adipate, allyl (meth)acrylate, vinyl crotonate, methylenebisacrylamide, hexanediol diacrylate, pentaerythritol diacrylate and trimethylolpropane triacrylate.
• the aqueous polymer dispersions employed in the present process will also generally contain one or more stabilizers in the form of emulsifiers, in particular nonionic emulsifiers and/or anionic emulsifiers, and/or protective colloids. Mixtures of different stabilizers can also be employed. The amount of stabilizer present in the polymer dispersion may be from 0.5 to 10 weight % of the total dispersion. Coating Compositions
• the aqueous polymer dispersions described above are combined with various adjuvants to produce coating compositions suitable for use as adhesives, paints, lacquers, varnishes and wood stains.
• the aqueous polymer dispersions are typically combined with one or more conventional fillers and/or pigments.
• pigments are understood as solids which have a refractive index greater than or equal to 1.75
• fillers are understood as meaning solids which have a refractive index of less than 1.75.
• Preferred fillers useful in the paint compositions herein can be, for example, calcium carbonate, magnesite, dolomite, kaolin, mica, talc, silica, calcium sulfate, feldspar, barium sulfate and opaque polymers.
• white pigments useful in the paint compositions herein can be zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide, lithopone (zinc sulfide+barium sulfate) and, preferably, titanium dioxide.
• inorganic colored pigments which may preferably be used in the paint compositions herein include iron oxides, carbon black, graphite, luminescent pigments, zinc yellow, zinc green, Paris blue, ultramarine, manganese black, antimony black, manganese violet, bismuth vanadate or Schweinfurt green.
• Suitable organic colored pigments preferably are, for example, sepia, gamboge, Cassel brown, toluidine red, para red, Hansa yellow, indigo, azo dyes, anthraquinone and indigo dyes as well as dioxazine, quinacridone, phthalocyanin, isoindolinone and metal complex pigments of the azomethine series.
• the fillers may be used as individual components. Mixtures of fillers such as, for example, calcium carbonate/kaolin and calcium carbonate/kaolin/talc have also been found to be particularly useful in practice. To increase the hiding power of the coating and to save on titanium dioxide, finely divided fillers such as, for example, finely divided calcium carbonate and mixtures of various calcium carbonates with different particle size distribution are frequently used.
• the fillers are mixed with appropriate amounts of white pigment and inorganic and/or organic colored pigments.
• auxiliaries based on anionic or non-ionic wetting agents such as preferably, for example, sodium pyrophosphate, sodium polyphosphate, naphthalenesulfonate, sodium polyacrylate, sodium polymaleinates and polyphosphonates such as sodium l-hydroxyethane-l,l-diphosphonate and sodium nitrilotris(methylenephosphonate), may be added.
• Thickeners may also be added to the paint formulations herein.
• Thickeners which may be used include, inter alia, sodium polyacrylate and water-soluble copolymers based on acrylic and methacrylic acid, such as acrylic acid/acrylamide and methacrylic acid/acrylic ester copolymers.
• Hydrophobically-modified alkali soluble (acrylic) emulsions HASE
• hydrophobically-modified ethoxylate (poly)urethanes HEUR
• hydrophobically-modified ethoxylate (poly)urethane alkali-swellable/soluble emulsions HEURASE
• poly ether polyols PEPO
• polyuria cellulose ether based thickeners
• Inorganic thickeners such as, for example, bentonites or hectorite, may also be used.
• Paint compositions produced herein are preferably free of any organic solvent, plasticizer or coalescent agent, namely so as to have a VOC content of less than 30g/l, preferably less than lg/l, of the paint composition.
• aqueous polymer dispersions having a pH ⁇ 7 the vinyl acetate/ethylene copolymer dispersion Mowilith LDM 1871 and the vinyl acetate/ethylene/vinyl decanoate dispersion Mowilith LDM 1828 from Celanese were produced without the addition of preservatives/biocides.
• the properties of the dispersions are listed in Table 1.
• a mixture of the following bacteria, yeasts and fungi /moulds are used for the preparation of the inoculum:
• Aeromonas hydrophila (sorbia, BAM 485)
• the microbial contamination remaining in the samples is determined by streaking the samples out onto Trypticase Sel Agar (TSA) and on Malt Extra Agar (MEA) as nutrient media and incubated at 30°C for 7 days.
• the level of growing is measured by using a rating of 0 for no growth up to a rating of 3 for full growth.
• the test is passed in case no growth is observed which means a rating of 0 on TSA and MEA nutrient media.
• After passing the first challenge cycle the test is repeated up to six times by adding again the inoculum to the sample and measuring the growth on TSA and MEA again as described. A sufficient protection is given in case a sample pass 6 challenge cycles.
• Paints were produced from the dispersions listed in Table 2 according to the following recipe: Ingredients Supplier p. b. w.

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• 2019
  • 2019-09-19 CN CN201980065345.6A patent/CN112839515B/zh active Active
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